Process of producing sulphur compounds



vthe resulting Patented D em 15, 1931 ERNST M. JOHANSEN, 0]! FALL rnocnssns CORPORATION, or AWARE No Drawing. Application 1115a June 22,

This invention relates to a ducingsulphur compounds.

One object of the invention is to provide a novel process for producing sulphur compounds from unsaturated hydrocarbons.

A further object of the invention is to proprocess of provide a novel process for producing sulphur compounds having the characteristic properties of mercaptans, and more'partlcularly a process for the production of such sulphur compounds from unsaturated hydrocarbons contained'in or derived from petroleum or natural gas. 7

In accordance with the preferred process unsaturated 'hyrocarbons, preferably contained in a hydrocarbon fraction from pe-' troleum, are caused to react with hydrogen sulphide at ordinary temperature, preferably by introducing the hydrogen sulphide into the hydrocarbon fraction, treatment with a reagent such as sulphuric acid or an adsorbent such as fullers earth, whereby sulphur compounds are formed having properties characteristic of the mercaptans. In the preferred process the introduction of the hydrogen sulphide is preferably continued for some period of true, and then solution agitated with sulphuric acid, preferably of -93%, until the odor of the hydrogen sulphide has disappeared. The hydrocarbons are again saturated with hydrogen sulphide and subsequently agitated with sulphuric acidand the treatment repeated preferably until no more reaction takes d place.- The sulphuric acid is then allowed to settle and is withdrawn from the resulting solution and then any free acid present is neutralized with a solution of alkali, preferably with a 10% solution of droxide. Thereafter the solution is washed with water'to remove the free alkali. The resulting solution is then subjected to distillation and redistillation to eliminate any nonvolatile substances present, and the distillate comprises a solution of the sulphur compounds, which I have found to possess characteristic mercaptan reactions.

The nature of the reaction between the unsaturated h drooarbons' and the hydrogen sulphide is believed to be a direct addition drocarbons and hydrogen following this by sodium hy-.

, liquid, and the RIVER, MASSACHUSETTS, ASSIG'NOR TO THE GRAY NEWARK, NEW JERSEY, A CORPORATION OF DEL- rnocrss or rnonuome sunrnun comounns 1926. Serial No. 117,866.

of the hydrogen sulphide and may be illustrated by the formation of ethyl mercaptan from ethylene and hydrogen sulphide according to the following e uation and in which ethylene may be regar ed asetypioal of any of the unsaturated hydrocarbons:

2 14 H S O H SH I have found that the sulphur compounds the character of mercaptans are produced causing reaction between unsaturated hyof y peratures varying'from 32 F. to 100 F. by exposing a solution containing hydrocarbons, partly or wholly saturated with hydrogen sulphide, to the action of various reagents such as mineral acids or. solid adsorbents such as fullers earth, charcoal or silica gel, either of which I believe to act as catalyzers. I prefer, however, to utilizer a small volume of a solution of sulphuric acid containing from 50-93% sulphuric acid.

y a more specific example of the present process, cracked captans and having a boiling range from 118 to 425 F a. sulphur content of 0.24%, and a content of 42% by volume removable by treatment with sulphuric acid of 93% H SO is treated in the manner above described'with hydrogen sulphide and then agi tated with 5% by volume of sulphuricacid containing rogen sulphide has disappeared. Successive treatments with hydrogen sulphide and acid are repeated until four treatments have been given. The sulphuric acid layer is allowed to settle after each treatment and is withdrawn or separated from the remaining liquid thus obtained isthen washed after the fourth treatment with a 10% solution of sodium hydroxide followed a hydrocarbon fraction from a petroleum distillate, free from mer-' H SO. until-the odor of hy-' sulphide at temby washing with water. The liquid is then I late contains now 3.6% sulphur, an amount corresponding to about 14% mercaptans.

The sulphur compounds produced and present in the distillate appear to be identical with those compounds recognized as present in various grades of crude petroleum and petroleum products, and known in the art of petroleum refining as sour sulphur compounds.

For certain purposes the solution of the sulphur com ounds in the hydrocarbons, produced as a ove described, may be used direetly, or, if desired, may be concentrated or the mercaptans obtained in a purer form by fractional distillation. The solution may be utilized for the production of mercaptides, thus enabling the separation from the hydrocarbons, and the isolation of the mercaptans themselves.

The product or products of the present process may be utilized for all of the purposes for which mercaptans of correspondmg purity are at present used.

While the invention is preferably applied to the process herein described, it is to be understood that it may be a plied to other processes within the scope 0 the following claims. y

Having thus described the invention, what is claimed is A 1. In a process forproducingsulphur compounds the step which comprises subjecting anunsaturated hydrocarbon to the action of hydrogen sulphide at ordinary temperatures in the presence of a mineral acid.

2. The process for producing sulphur comounds which comprises repeatedly subi'ectmg hydrocarbon material comprised at east in part' of unsaturated hydrocarbon to the action of hydrogen sulphide at ordinary tem- 'peratures in the presence of a mineral acid,

separating the acid layer, neutralizing an free acid remaining in the material with a kali, and then separating the resulting sulphur compounds from the non-reacting components of the hydrocarbon.

3. The process for producing sulphur compounds which comprisesrepeat'edly subjecting hydrocarbon material comprised at-least in part of unsaturated hydrocarbons to the action ofi hydrogen sulphide at ordinary temperatures in the presence of sulphuric acid, separating the acid layer, neutralizing-"an free acid remaining in the material with .a

kali, and then separating the resultingfl sulphur compounds from the non-reacting components of the hydrocarbon.

4. The process for producing sulphur compounds which comprises efiecting reaction etween hydrocarbon material comprised at least in part of unsaturated hydrocarbons,

and hydrogen sulphide at a temperature between 32 and 100 F. and in the presence of a mineral acid.

5. The process of producing mercaptans by the catalytic interaction of hydrogen sulphide and olefins.

6. The'process of producing mercaptans by the catalytic interaction of hydrogen sulphide and liquid olefins.

In testimony whereof, I have hereunto subscribed my name this 17 day of June 1926.

ERNST M. JoHANshN. 

